CN118028601A - Novel method for preferentially extracting lithium from waste ternary lithium ion battery - Google Patents
Novel method for preferentially extracting lithium from waste ternary lithium ion battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002386 leaching Methods 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000005238 degreasing Methods 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229940073644 nickel Drugs 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 claims 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Abstract
The invention relates to the technical field of preferential lithium extraction from waste ternary lithium ion batteries, in particular to a novel method for preferential lithium extraction from waste ternary lithium ion batteries. Which comprises the following steps: and mixing the waste lithium ion battery anode powder with activated carbon subjected to adsorption degreasing in a wastewater treatment working section according to a proportion. According to the invention, the anode material of the waste ternary lithium ion battery is mixed with activated carbon subjected to adsorption and degreasing in a wastewater working section, the mixture is placed in an atmosphere furnace for high-temperature roasting, the roasted product is soaked in water and carbon dioxide is introduced, filtrate and filter residues are separated after a period of time, the filtrate is heated and decomposed to prepare a lithium carbonate product, nickel, cobalt and manganese are recovered from the filter residues through the processes of leaching, impurity removal, extraction and evaporative crystallization, lithium metal in the waste ternary lithium battery is preferentially extracted by adopting carbothermic reduction, the efficient recovery of lithium metal is realized, the activated carbon subjected to adsorption and degreasing can be reused, the carbothermic reduction efficiency is improved, and the purity of the obtained lithium solution is high.
Description
Technical Field
The invention relates to the technical field of preferential lithium extraction from waste ternary lithium ion batteries, in particular to a novel method for preferential lithium extraction from waste ternary lithium ion batteries.
Background
The lithium ion battery has wide application, the use amount is rapidly increased, meanwhile, the scrapped amount is also increased increasingly, the high-efficiency recycling of the scrapped lithium battery becomes an important problem which is urgent to be solved at present in China, the scrapped power battery contains a large amount of valuable metals, and the scrapped power battery is discarded and treated at will, so that not only is the cobalt, nickel, manganese, lithium and other resources wasted greatly, but also the environment is polluted seriously, and therefore, the development of a green pollution-free treatment method capable of realizing large-scale industrialization is needed.
Wherein, chinese patent application number is: 201910192899.4 discloses a method for recovering valuable metals from waste lithium ion battery materials, which comprises the steps of mixing a waste lithium ion battery anode material with sulfur, sulfide and other low-valence sulfates, carrying out vulcanization roasting treatment at 300-900 ℃, leaching a roasting product by water to obtain a lithium salt aqueous solution, further preparing a lithium carbonate product, leaching the leaching residue by oxidation acid leaching or direct acid leaching to obtain valuable elements such as nickel, cobalt and manganese, and purifying and extracting the leaching solution to obtain corresponding cobalt salt and nickel salt products. The method has simple process and short flow, the sulfur dioxide gas generated after the roasting of the sulfide can be used for preparing sulfuric acid, the sulfuric acid is used for subsequent nickel-cobalt leaching, zero pollution emission is realized, and finally the purpose of high-efficiency low-cost comprehensive recovery of valuable metals in the positive electrode material of the lithium ion battery is achieved.
The method has the problems that sulfide roasting is adopted, and the roasted flue gas contains a large amount of toxic and harmful gases such as sulfur dioxide or sulfur trioxide and the like, so that further purification treatment is needed; meanwhile, the recovery rate of the final lithium salt is low, and the purity of other metals such as nickel cobalt manganese salt solution can not reach the battery level standard, so that the lithium salt solution is difficult to be directly used for remanufacturing the ternary lithium ion battery anode material.
Secondly, the existing waste lithium battery recovery technology comprises three kinds of fire, wet and biological methods, wherein the research and application of the wet recovery technology are the most extensive, the wet recovery of valuable metals in the waste lithium battery mainly comprises three main working sections of pretreatment, leaching and extraction, and the lithium metal recovery adopts the back-end lithium extraction, namely the lithium recovery working procedure is positioned at the extreme end of the whole technological process, and because a plurality of working procedures of pretreatment, leaching, impurity removal purification, extraction and the like are carried out before the lithium extraction, the reduction of the lithium recovery rate, the low purity of products and the large amount of waste water are inevitably caused, thereby influencing the benefit of enterprises.
Therefore, in order to solve the problems of low recovery rate and low purity of the product, a simple and efficient method for preferentially extracting lithium is needed to solve the problems.
Meanwhile, in order to respond to the call of resource reuse, the used active carbon resource and the lithium extraction process can be combined, so that the problem of active carbon reuse is solved, and the purity of lithium extraction can be improved.
In view of this, a new method for preferentially extracting lithium from waste ternary lithium ion batteries is provided.
Disclosure of Invention
The invention aims to provide a novel method for preferentially extracting lithium from waste ternary lithium ion batteries, which aims to solve the problems that the prior art is low in lithium extraction rate and poor in extraction purity.
In order to achieve the above purpose, the invention provides a new method for preferentially extracting lithium from waste ternary lithium ion batteries, which comprises the following steps:
1. preferential lithium extraction
S1, mixing the waste lithium ion battery anode powder with activated carbon subjected to adsorption degreasing in a wastewater treatment working section according to a proportion;
S2, weighing the mixture in the quantitative S1, placing the mixture in a crucible, and placing the crucible in an atmosphere furnace to perform reduction roasting treatment at high temperature;
S3, after roasting, placing the roasting product obtained from the S2 into an aqueous solution, stirring the roasting product and the aqueous solution at room temperature, introducing carbon dioxide into the roasting product in the water leaching process for carbonization reaction, and filtering to obtain LiHCO3 filtrate and filter residues;
s4, carrying out heating decomposition on the LiHCO3 filtrate obtained in the S3 to prepare a lithium carbonate product;
2. Extracting nickel, cobalt and manganese
And S5, recovering nickel, cobalt and manganese from filter residues in the S3 through the processes of leaching, impurity removal, extraction and evaporative crystallization.
As a further improvement of the technical scheme, the activated carbon used in the step S1 is decomposed at high temperature to obtain carbon-based carbon dioxide.
As a further improvement of the technical scheme, the addition amount of the activated carbon after the adsorption and oil removal in the S1 is 0% -20% of the total mass of the waste lithium ion battery anode material.
As a further improvement of the technical scheme, the roasting temperature is set to be 400-700 ℃ in the step S2, and the roasting time is set to be 1-6 hours.
As a further improvement of the technical scheme, carbon dioxide generated in the roasting reduction process in the step S2 is introduced into the step S3, so that the carbon dioxide generated in the step S2 is used for carbonization reaction of the step S3.
As a further improvement of the technical scheme, the water temperature for water immersion in the step S3 is set to be 0-60 ℃, meanwhile, the water immersion time is set to be 1-5 hours, and the liquid-solid ratio in the step S3 is in the range of 4:1-10:1.
As a further improvement of the technical scheme, the temperature of the heating decomposition leaching solution in the step S4 is 60-100 ℃.
As a further improvement of the technical scheme, in the step S5, hydrochloric acid and an oxidant are added during leaching of the filter residues.
As a further improvement of the technical scheme, the leaching temperature in the leaching process of the filter residue in the step S5 is set to be 60-90 ℃, the leaching time of the filter residue is set to be 1-3 h, and meanwhile, the liquid-solid ratio is set to be 3:1-5:1, and the acid concentration is set to be 1-3 mol/L.
As a further improvement of the technical scheme, iron powder is added into the liquid after acid leaching in the step S5, the pH value is adjusted to 3.5-4.5, impurity iron and aluminum are removed by adopting a chemical precipitation method, a solution after impurity removal is obtained, and the solution after impurity removal is extracted by adopting a P204 extractant and a P507 extractant, so that corresponding nickel, cobalt and manganese sulfate solution is obtained.
Compared with the prior art, the invention has the beneficial effects that:
According to the novel method for preferentially extracting lithium from the waste ternary lithium ion battery, the positive electrode material of the waste ternary lithium ion battery is mixed with activated carbon subjected to adsorption degreasing in a waste water working section, the mixture is placed in an atmosphere furnace for high-temperature roasting, a roasted product is soaked in water and introduced with carbon dioxide, filtrate and filter residues are separated after a period of time, the filtrate is heated and decomposed to obtain a lithium carbonate product, preferential extraction of lithium is completed, the filter residues are subjected to acid leaching by adopting an acidic solution with a certain concentration to obtain a nickel, cobalt and manganese sulfate solution, lithium metal in the waste ternary lithium battery is preferentially extracted by adopting carbon thermal reduction through processes such as impurity removal, extraction, evaporative crystallization and the like, the process flow is shortened, the activated carbon subjected to adsorption degreasing can be reused, the carbon thermal reduction efficiency is improved, the purity of the obtained lithium solution is high, and then the lithium product with high quality can be obtained.
Drawings
FIG. 1 is a schematic overall flow diagram of an embodiment of the present invention;
FIG. 2 is an overall process flow diagram of an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
Thus, the following detailed description of the embodiments of the application, as presented in the figures, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present application and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present application, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
Referring to fig. 1-2, the present embodiment provides a new method for preferentially extracting lithium from waste ternary lithium ion batteries, which includes the following steps:
1. preferential lithium extraction
S1, mixing the waste lithium ion battery anode powder with activated carbon subjected to adsorption degreasing in a wastewater treatment working section according to a proportion;
The addition amount of the activated carbon after adsorption and degreasing in the S1 is 0-20% of the total mass of the waste lithium ion battery anode material, and different percentages of the activated carbon after adsorption and degreasing and the waste lithium ion battery anode material can be mixed according to requirements, for example, 0% of the activated carbon after adsorption and degreasing, 10% of the activated carbon after adsorption and degreasing or 20% of the activated carbon after adsorption and degreasing are added, and different leaching rates of lithium can be obtained by adding different proportions of the activated carbon after adsorption and degreasing.
For example, 0% of activated carbon after oil removal by adsorption is added into the waste ternary positive electrode powder according to the mass ratio, and the two are uniformly mixed to obtain a mixture.
The following chemical formula can be used for lithium extraction:
6LiNi 1/3Co1/3Mn1/3O2+7/2C→2Co+2Ni+2MnO+3Li2CO3+1/2CO2；
6LiNi1/3Co1/3Mn1/3O2: positive electrode active material in ternary lithium ion battery, wherein lithium (Li), nickel (Ni), cobalt (Co) and manganese (Mn) are metal elements, oxygen (O) is oxygen element, 7/2C: graphite or coke is used as a reducing agent.
2Co: 2 simple substances of cobalt (Co) after the reaction;
2N i: 2 simple substances of nickel (Ni) after the reaction;
2MnO: 2 manganese dioxide (MnO) after the reaction;
3L i2CO3: 3 lithium carbonate (Li 2CO 3) after the reaction;
1/2CO2: 1/2 carbon dioxide (CO 2) generated after the reaction.
The chemical reaction represents the process of extracting lithium and other metal elements from the waste ternary lithium ion battery, wherein the ternary lithium ion battery is a battery widely applied to electric automobiles and electronic equipment, and the positive electrode material is generally composed of metal elements such as lithium, nickel, cobalt, manganese and the like, and the quantity and quality of the extract can be effectively controlled by controlling the reaction conditions and the formula;
I.e. 6LiNi1/3Co1/3Mn1/3O2 and 7/2C on the left are starting materials for the reaction, while 2Co, 2Ni, 2MnO, 3Li2CO3 and 1/2CO2 on the right are the final products of the reaction.
S2, weighing the mixture in the quantitative S1, placing the mixture in a crucible, and placing the crucible in an atmosphere furnace to perform reduction roasting treatment at high temperature;
Setting the roasting temperature at 400-700 ℃ and the roasting time at 1-6 hours in the step S2, for example, heating an atmosphere furnace to 600 ℃ at a heating rate of 5 ℃/min, and setting the roasting time at 5 hours to roast the mixture in the crucible.
And (3) decomposing the activated carbon used in the step S1 at high temperature in the roasting process to obtain carbon-based carbon dioxide, so as to further promote carbothermic reduction and realize waste utilization.
And S3, after roasting, placing the roasting product obtained from the step S2 in an aqueous solution, stirring the roasting product and the aqueous solution at room temperature, introducing carbon dioxide in the leaching process of the roasting product for carbonization reaction, and filtering to obtain (LiHCO 3) filtrate and filter residues, wherein the LiHCO3 is lithium bicarbonate.
Wherein the water temperature for water immersion in S3 is set to 0-60 ℃, and the water immersion time is set to 1-5 hours.
Further, the liquid-solid ratio in the step S3 is in the range of 4:1-10:1.
For example, the liquid-solid ratio is set to be 6:1, the water immersion time is 1h, namely, the water solution is 6, the roasting product is 1, the water immersion time of the two is one hour, and carbon dioxide is introduced into the two for water immersion time, so that carbonization reaction is carried out.
In order to utilize the carbon dioxide, the carbon dioxide generated in the roasting reduction process in the step S2 is introduced into the step S3, and the carbon dioxide generated in the step S2 is used for the carbonization reaction of the step S3.
S4, carrying out heating decomposition on the LiHCO3 filtrate obtained in the S3 to prepare a lithium carbonate product;
In addition, the temperature of the heating decomposition leaching solution in the step S4 is 60-100 DEG C
And in the decomposition process, lithium bicarbonate in the filtrate is decomposed into lithium carbonate and water vapor, and a pure lithium carbonate product is finally obtained.
For example, combining the above cases, adding 0% of activated carbon after adsorption and degreasing into the waste ternary positive electrode powder according to the mass ratio, uniformly mixing, weighing a quantitative mixed material, placing the quantitative mixed material into a crucible, moving the crucible into an atmosphere furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, roasting for 5 hours, placing a roasted product into an aqueous solution after roasting, stirring at room temperature, wherein the liquid-solid ratio is 6:1, the water leaching time is 1 hour, introducing CO 2 during the water leaching process, filtering after the reaction is finished, drying filter residues, and analyzing to obtain the lithium leaching rate.
2. Extracting nickel, cobalt and manganese
And S5, recycling nickel, cobalt and manganese from the residual filter residues in the S3 through the working procedures of leaching, impurity removal, extraction and evaporative crystallization.
Wherein, the leaching process of the water leaching slag can use one or more of hydrochloric acid, nitric acid or sulfuric acid, and the oxidant can use one or more of hydrogen peroxide and sodium metabisulfite.
And S5, in the leaching process of filter residues in the step of leaching, the leaching temperature is 60-90 ℃, the leaching time is 1-3 h, the liquid-solid ratio is 3:1-5:1, the acid concentration is 1-3 mol/L, one or more of iron powder and manganese powder are added into the acid leaching solution to remove copper, the pH value is adjusted to 3.5-4.5, the impurity iron and aluminum are removed by adopting a chemical precipitation method, and after the obtained filtrate after the impurity removal, the P204 (di (2-ethylhexyl) phosphate) is adopted to extract manganese and the P507 (P507 phosphate extractant) are adopted to extract nickel and cobalt respectively, so that corresponding nickel, cobalt and manganese sulfate solutions are obtained.
And (3) adding the filter residue remained after the preferential lithium extraction into 2mol/L sulfuric acid solution according to a liquid-solid ratio of 4:1, leaching for 3 hours at a temperature of 75 ℃, and filtering to obtain a sulfate solution of nickel, cobalt and manganese.
The working principle of a new method for preferentially extracting lithium from waste ternary lithium ion batteries is as follows: adding 0% of activated carbon subjected to adsorption degreasing or 10% of activated carbon subjected to adsorption degreasing or 20% of activated carbon subjected to adsorption degreasing into the waste ternary positive electrode powder according to the mass ratio, uniformly mixing, wherein the steps of mixing the activated carbon subjected to adsorption degreasing with the waste ternary positive electrode powder in different percentages are the same;
Firstly, weighing quantitative mixed materials, placing the quantitative mixed materials into a crucible, moving the crucible into an atmosphere furnace, heating the crucible to 600 ℃ at a heating rate of 5 ℃/min, roasting for 5 hours, placing a roasted product into an aqueous solution after roasting is finished, stirring at room temperature, wherein the liquid-solid ratio is 6:1, leaching for 1 hour, introducing carbon dioxide generated by pyrolysis in the leaching process, filtering after the reaction is finished, drying filter residues, and analyzing to obtain the lithium leaching rate;
And adding the filter residue into 2mol/L sulfuric acid solution according to a liquid-solid ratio of 4:1, leaching for 3 hours at 75 ℃, filtering to obtain sulfate solution of nickel, cobalt and manganese, and analyzing to obtain leaching rates of nickel, cobalt and manganese.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The novel method for preferentially extracting lithium from the waste ternary lithium ion battery is characterized by comprising the following steps of:
1. preferential lithium extraction
S1, mixing the waste lithium ion battery anode powder with activated carbon subjected to adsorption degreasing in a wastewater treatment working section according to a proportion;
S2, weighing the mixture in the quantitative S1, placing the mixture in a crucible, and placing the crucible in an atmosphere furnace to perform reduction roasting treatment at high temperature;
S3, after roasting, placing the roasting product obtained from the S2 into an aqueous solution, stirring the roasting product and the aqueous solution at room temperature, introducing carbon dioxide into the roasting product in the water leaching process for carbonization reaction, and filtering to obtain LiHCO3 filtrate and filter residues;
s4, carrying out heating decomposition on the LiHCO3 filtrate obtained in the S3 to prepare a lithium carbonate product;
2. Extracting nickel, cobalt and manganese
And S5, recovering nickel, cobalt and manganese from filter residues in the S3 through the processes of leaching, impurity removal, extraction and evaporative crystallization.
2. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 1, which is characterized in that: and (2) decomposing the activated carbon used in the step (S1) at high temperature to obtain carbon and carbon dioxide.
3. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 2, which is characterized in that: the addition amount of the activated carbon after the adsorption and oil removal in the S1 is 0-20% of the total mass of the waste lithium ion battery anode material.
4. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 1, which is characterized in that: setting the roasting temperature in the step S2 to be 400-700 ℃ and setting the roasting time to be 1-6 hours.
5. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 4, wherein the method is characterized in that: and (3) introducing the carbon dioxide generated in the roasting reduction process in the step S2 into the step S3, so that the carbon dioxide generated in the step S2 is used for carbonization reaction of the step S3.
6. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 1, which is characterized in that: the water temperature for water immersion in the step S3 is set to be 0-60 ℃, the water immersion time is set to be 1-5 hours, and the liquid-solid ratio in the step S3 ranges from 4:1 to 10:1.
7. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 1, which is characterized in that: the temperature of the heating decomposition leaching solution in the step S4 is 60-100 ℃.
8. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 1, which is characterized in that: in the step S5, hydrochloric acid and an oxidant are added when the filter residues are leached.
9. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 8, wherein the method is characterized in that: setting the leaching temperature in the leaching process of the filter residue in the step S5 to be 60-90 ℃, setting the leaching time of the filter residue to be 1-3 h, and setting the liquid-solid ratio to be 3:1-5:1 and the acid concentration to be 1-3 mol/L.
10. The novel method for preferentially extracting lithium from waste ternary lithium ion batteries according to claim 9, wherein the method is characterized in that: and (3) adding iron powder into the liquid subjected to acid leaching in the step (S5), adjusting the pH value to 3.5-4.5, removing impurity iron and aluminum by adopting a chemical precipitation method to obtain a solution subjected to impurity removal, and extracting the solution subjected to impurity removal by adopting a P204 extractant and a P507 extractant to obtain corresponding nickel, cobalt and manganese sulfate solution.
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